FR2959998A1 - TERNARY HEAT TRANSFER FLUIDS COMPRISING DIFLUOROMETHANE, PENTAFLUOROETHANE AND TETRAFLUOROPROPENE - Google Patents

Abstract

The invention relates to a ternary composition comprising: - from 5 to 50% of difluoromethane; from 2 to 20% of pentafluoroethane; and 30 to 90% of tetrafluoropropene. The tetrafluoropropene may be 1,3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene. This composition can be used as a heat transfer fluid in a vapor compression circuit.

Description

1 TERNARY HEAT TRANSFER FLUIDS COMPRISING DIFLUOROMETHANE, PENTAFLUOROETHANE AND TETRAFLUOROPROPENE

FIELD OF THE INVENTION The present invention relates to transfer fluids based on difluoromethane, pentafluoroethane and tetrafluoropropene, which exhibit high performance and low GWP, and are therefore suitable for replacing conventional refrigerants.

BACKGROUND Fluorocarbon-based fluids are widely used in vapor compression heat transfer systems, including air conditioning, heat pump, refrigeration or freezing devices. These devices have in common to rely on a thermodynamic cycle comprising the vaporization of the fluid at low pressure (in which the fluid absorbs heat); compressing the vaporized fluid to a high pressure; condensing the vaporized fluid into a high pressure liquid (in which the fluid emits heat); and the expansion of the fluid to complete the cycle. The choice of a heat transfer fluid (which may be a pure compound or a mixture of compounds) is dictated on the one hand by the thermodynamic properties of the fluid, and on the other hand by additional constraints. Thus, a particularly important criterion is that of the impact of the fluid considered on the environment. In particular, chlorinated compounds (chlorofluorocarbons and hydrochlorofluorocarbons) have the disadvantage of damaging the ozone layer. Thus, non-chlorinated compounds such as hydrofluorocarbons, fluoroethers and fluoroolefins are now generally preferred. Currently used heat transfer fluids are HFC-134a, R404a (ternary mixture of 52% HFC-143a, 44% HFC-125 and 4% HFC-134a) and R407c (ternary mixture of 52% HFC-134a, 25% HFC-125 and 23% HFC-32). However, it is necessary to develop other heat transfer fluids having a global warming potential (GWP) lower than that of the above fluids, and having equivalent performance and preferably improved. US 2009/0250650 discloses various fluoroolefin compositions and their use as heat transfer fluids. In particular, the document describes the mixture consisting of HFC-32, HFC-125 and HFO-1234ze as well as the mixture consisting of HFC-32, HFC-125 and HFO-1234yf. The compositions indicated as preferred are the following: 23% of HFC-32, 25% of HFC-125 and 52% of HFO-1234ze; - 30% HFC-32, 50% HFC-125 and 20% HFO-1234ze; 40% HFC-32, 50% HFC-125 and 10% HFO-1234yf; 23% HFC-32, 25% HFC-125 and 52% HFO-1234yf; 15% HFC-32, 45% HFC-125 and 40% HFO-1234yf; and 10% HFC-32, 60% HFC-125 and 30% HFO-1234yf. WO 2010/002014 discloses a non-flammable refrigerant based on HFC-32, HFC-125 and HFO-1234yf. Several compositions are disclosed, in particular that comprising 15% HFC-32, 25% HFC-125 and 60% HFO-1234yf. However, there is still a need to develop other heat transfer fluids having a relatively low GWP, and having better energy performance than the heat transfer fluids of the state of the art.

SUMMARY OF THE INVENTION The invention firstly relates to a ternary composition comprising: from 5 to 50% of difluoromethane; from 2 to 20% of pentafluoroethane; and 30 to 90% of tetrafluoropropene. According to one embodiment, the tetrafluoropropene is 1,3,3,3-tetrafluoropropene. In another embodiment, the tetrafluoropropene is 2,3,3,3-tetrafluoropropene. According to one embodiment, the composition comprises: from 15 to 35% of difluoromethane; from 5 to 20% of pentafluoroethane; and from 45 to 80% 2,3,3,3-tetrafluoropropene; and preferably: 18 to 25% difluoromethane; from 8 to 20% of pentafluoroethane; and from 55 to 74% 2,3,3,3-tetrafluoropropene; According to one embodiment, the composition comprises: from 15 to 50% of difluoromethane; ~ o - 5 to 20% pentafluoroethane; and from 30 to 80% of 1,3,3,3-tetrafluoropropene; and preferably: from 30 to 40% difluoromethane; from 8 to 20% of pentafluoroethane; and 40-62% 1,3,3,3-tetrafluoropropene. According to one embodiment, the composition comprises: from 5 to 30% of difluoromethane; from 5 to 20% of pentafluoroethane; and from 50 to 90% of 1,3,3,3-tetrafluoropropene; And preferably: from 5 to 20% difluoromethane; from 5 to 20% of pentafluoroethane; and from 60 to 90% of 1,3,3,3-tetrafluoropropene. According to one embodiment, the composition comprises: from 20 to 40% of difluoromethane; from 5 to 20% of pentafluoroethane; and from 40 to 75% of 1,3,3,3-tetrafluoropropene; and preferably: 25 to 40% difluoromethane; 5- to 20% pentafluoroethane; and from 40 to 70% of 1,3,3,3-tetrafluoropropene. The invention also relates to the use of the aforementioned ternary composition as a heat transfer fluid in a vapor compression circuit. The invention also relates to a heat transfer composition comprising the aforementioned ternary composition as a heat transfer fluid, and one or more additives selected from lubricants, stabilizers, surfactants, tracer agents, fluorescers, odorants, solubilizers and mixtures thereof. The invention also relates to a heat transfer installation comprising a vapor compression circuit containing the aforementioned ternary composition as a heat transfer fluid, or containing a heat transfer composition as mentioned above. According to one embodiment, this installation is chosen from mobile or stationary installations for heat pump heating, air conditioning, refrigeration and freezing. The invention also relates to a method for heating or cooling a fluid or a body by means of a vapor compression circuit containing a heat transfer fluid, said method comprising successively the evaporation of the transfer fluid. heat, compressing the heat transfer fluid, condensing the heat fluid and expanding the heat transfer fluid, and the heat transfer fluid being the aforementioned ternary composition. According to one embodiment of the heating or cooling method, this method is a method of cooling a fluid or a body, wherein the temperature of the cooled fluid or body is -40 ° C to -10 ° C, and preferably from -35 ° C to -25 ° C, more preferably from -30 ° C to -20 ° C, and wherein the heat transfer fluid comprises: 15 to 35% difluoromethane from 5 to 20% of pentafluoroethane and from 45 to 80% of 2,3,3,3-tetrafluoropropene, preferably from 18 to 25% of difluoromethane, from 8 to 20% of pentafluoroethane and from 55 to 74% of 2 3,3,3-tetrafluoropropene; or 15 to 50% of difluoromethane, 5 to 20% of pentafluoroethane and 30 to 80% of 1,3,3,3-tetrafluoropropene, preferably 30 to 40% of difluoromethane, 8 to 20% of pentafluoroethane and from 40 to 62% 1,3,3,3-tetrafluoropropene. According to another embodiment of the heating or cooling process, this method is a method of cooling a fluid or a body, wherein the temperature of the fluid or cooled body is -15 ° C to 15 ° C, and preferably from -10 ° C to 10 ° C, more preferably from -5 ° C to 5 ° C, and wherein the heat transfer fluid comprises: 15 to 35% difluoromethane, 5 to 20% of pentafluoroethane and 45 to 80% of 2,3,3,3-tetrafluoropropene, preferably 18 to 25% of difluoromethane, 8 to 20% of pentafluoroethane and 55 to 74% of 2,3 3,3-tetrafluoropropene; or 5 to 30% of difluoromethane, 5 to 20% of pentafluoroethane and 50 to 90% of 1,3,3,3-tetrafluoropropene, preferably 5 to 20% of difluoromethane, 5 to 20% of pentafluoroethane and from 60 to 90% 1,3,3,3-tetrafluoropropene; or 20 to 40% of difluoromethane, 5 to 20% of pentafluoroethane and 40 to 75% of 1,3,3,3-tetrafluoropropene, preferably 25 to 40% of difluoromethane, 5 to 20% of pentafluoroethane and 40 to 70% 1,3,3,3-tetrafluoropropene. According to another embodiment of the heating or cooling process, this method is a method of heating a fluid or a body, wherein the temperature of the fluid or heated body is 30 ° C to 80 ° C and preferably from 35 ° C to 55 ° C, more preferably from 40 ° C to 50 ° C, and wherein the heat transfer fluid comprises: 15 to 35% difluoromethane, 5 to 20 % of pentafluoroethane and 45 to 80% of 2,3,3,3-tetrafluoropropene, preferably 18 to 25% of difluoromethane, 8 to 20% of pentafluoroethane and 55 to 74% of 2,3,3, 3-tetrafluoropropene; or 5 to 30% of difluoromethane, 5 to 20% of pentafluoroethane and 50 to 90% of 1,3,3,3-tetrafluoropropene, preferably 5 to 20% of difluoromethane, 5 to 20% of pentafluoroethane and from 60 to 90% 1,3,3,3-tetrafluoropropene; or 20 to 40% of difluoromethane, 5 to 20% of pentafluoroethane and 40 to 75% of 1,3,3,3-tetrafluoropropene, preferably 25 to 40% of difluoromethane, 5 to 20% of pentafluoroethane and 40 to 70% 1,3,3,3-tetrafluoropropene. The invention also relates to a method for reducing the environmental impact of a heat transfer installation comprising a vapor compression circuit containing an initial heat transfer fluid, said method comprising a step of replacing the heat transfer fluid. initial heat in the vapor compression circuit by a final transfer fluid, the final transfer fluid having a GWP lower than the initial heat transfer fluid, wherein the final heat transfer fluid is the aforementioned ternary composition. According to one embodiment of this method of reducing the environmental impact, the initial heat transfer fluid is a ternary mixture of 52% of 1,1,1-trifluoroethane, 44% of pentafluoroethane and 4% of 1 , 1,1,2-tetrafluoroethane or a ternary mixture of 52% 1,1,1,2-tetrafluoroethane, 25% pentafluoroethane and 23% difluoromethane, and the final heat transfer fluid comprises: 35% difluoromethane, 5 to 20% pentafluoroethane and 45 to 80% 2,3,3,3-tetrafluoropropene, preferably 18 to 25% difluoromethane, 8 to 20% pentafluoroethane and 74% 2,3,3,3-tetrafluoropropene; or 15 to 50% of difluoromethane, 5 to 20% of pentafluoroethane and 30 to 80% of 1,3,3,3-tetrafluoropropene, preferably 30 to 40% of difluoromethane, 8 to 20% of pentafluoroethane and from 40 to 62% 1,3,3,3-tetrafluoropropene; or 20 to 40% of difluoromethane, 5 to 20% of pentafluoroethane and 40 to 75% of 1,3,3,3-tetrafluoropropene, preferably 25 to 40% of difluoromethane, 5 to 20% of pentafluoroethane and 40 to 70% 1,3,3,3-tetrafluoropropene. According to another embodiment of this method of reducing the environmental impact, the initial heat transfer fluid is 1,1,1,2-tetrafluoroethane, and the final heat transfer fluid comprises: 30% of difluoromethane, 5 to 20% of pentafluoroethane and 50 to 90% of 1,3,3,3-tetrafluoropropene, preferably 5 to 20% of difluoromethane, 5 to 20% of pentafluoroethane and 60 to 90% 1,3,3,3-tetrafluoropropene.

The present invention overcomes the disadvantages of the state of the art. It provides more particularly heat transfer fluids having a relatively low GWP, and having better energy performance than known heat transfer fluids. This is accomplished through ternary mixtures comprising HFC-32, HFC-125 and tetrafluoropropene in the proportions indicated above.

According to some particular embodiments, the invention also has one or preferably more of the advantageous features listed below. The heat transfer fluids of the invention have a higher coefficient of performance than the reference refrigerants R404a, R407c and / or HFC-134, in the same type of applications. The capacity of the heat transfer fluids of the invention is greater than or equal to that of the reference refrigerants, same type of applications. Correlatively, the invention makes it possible to reduce the GWP of existing systems comprising one of the reference refrigerants above, and this to a large extent improving the performance of these systems, by replacing reference refrigerants with transfer fluids. of heat of the invention. The heat transfer fluids of the invention have a higher coefficient of performance than the ternary mixtures of HFC-32, HFC-125 and HFO-1234ze or HFO-1234yf which are described in documents US 2009/0250650 and WO 2010 / 002014. Certain heat transfer fluids according to the invention make it possible to obtain a temperature at the outlet of the compressor that is lower than that obtained with the heat transfer fluids of the state of the art. According to the invention, the global warming potential (GWP) is defined with respect to carbon dioxide and with respect to a duration of 100 years, according to the method indicated in "The scientific assessment of ozone depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION The invention is now described in more detail and in a nonlimiting manner in the description which follows. By "heat transfer compound" or "heat transfer fluid" (or refrigerant), is meant a compound, respectively a fluid, capable of absorbing heat by evaporating at low temperature and low pressure and to reject heat by condensing at high temperature and high pressure, in a vapor compression circuit. In general, a heat transfer fluid may comprise one, two, three or more than three heat transfer compounds. By "heat transfer composition" is meant a composition comprising a heat transfer fluid and optionally one or more additives which are not heat transfer compounds for the intended application. The heat transfer method according to the invention is based on the use of an installation comprising a vapor compression circuit which contains a heat transfer fluid. The heat transfer process may be a method of heating or cooling a fluid or a body. The vapor compression circuit containing a heat transfer fluid comprises at least one evaporator, a compressor, a condenser and an expander, as well as heat transfer fluid transport lines between these elements. The evaporator and the condenser comprise a heat exchanger allowing a heat exchange between the heat transfer fluid and another fluid or body. As a compressor, it is possible to use in particular a centrifugal compressor with one or more stages or a mini centrifugal compressor. Rotary, piston or screw compressors can also be used. The compressor may be driven by an electric motor or by a gas turbine (eg powered by vehicle exhaust, for mobile applications) or by gearing. The facility may include a turbine to generate electricity (Rankine cycle). The installation may also optionally include at least one coolant circuit used to transmit the heat (with or without change of state) between the heat transfer fluid circuit and the fluid or body to be heated or cooled.

The installation may also optionally include two or more vapor compression circuits containing identical or different heat transfer fluids. For example, the vapor compression circuits may be coupled together. The vapor compression circuit operates in a conventional vapor compression cycle. The cycle comprises changing the state of the heat transfer fluid from a liquid phase (or two-phase liquid / vapor) to a vapor phase at a relatively low pressure, and then compressing the fluid in the vapor phase to a relatively high pressure. high, the change of state (condensation) of the heat transfer fluid from the vapor phase to the liquid phase at a relatively high pressure, and the reduction of the pressure to restart the cycle In the case of a cooling process, the heat resulting from the fluid or the body that is cooled (directly or indirectly, via a coolant) is absorbed by the heat transfer fluid, during the evaporation of the latter, and at a relatively low temperature compared to the environment. Cooling processes include air conditioning processes (with mobile installations, for example in vehicles, or stationary), refrigeration and freezing or cryogenics. In the case of a heating process, heat is transferred (directly or indirectly via a heat transfer fluid) from the heat transfer fluid, during the condensation thereof, to the fluid or to the body that is heating, and this at a relatively high temperature compared to the environment. The installation to implement the heat transfer is called in this case "heat pump". It is possible to use any type of heat exchanger for the implementation of the heat transfer fluids according to the invention, and in particular co-current heat exchangers. However, according to a preferred embodiment, the invention provides that the cooling and heating processes, and the corresponding facilities, comprise a countercurrent heat exchanger, either the condenser or the evaporator. Indeed, the heat transfer fluids according to the invention are particularly effective with countercurrent heat exchangers. Preferably, both the evaporator and the condenser comprise a countercurrent heat exchanger. According to the invention, the term "countercurrent heat exchanger" is understood to mean a heat exchanger in which heat is exchanged between a first fluid and a second fluid, the first fluid at the inlet of the exchanger exchanging heat with the second fluid at the outlet of the exchanger, and the first fluid at the outlet of the exchanger exchanging heat with the second fluid at the inlet of the exchanger.

For example, countercurrent heat exchangers include devices in which the flow of the first fluid and the flow of the second fluid are in opposite or almost opposite directions. The exchangers operating in cross current mode with countercurrent tendency are also included among the countercurrent heat exchangers within the meaning of the present application. The meaning of the various abbreviations used to designate the various chemical compounds mentioned in the application is as follows: HFC-134a: 1,1,1,2-tetrafluoroethane; HFC-125: pentafluoroethane; - HFC-32: difluoromethane; HFO-1234ze: 1,3,3,3-tetrafluoropropene; HFO-1234yf: 2,3,3,3-tetrafluoropropene. The heat transfer fluids used in the invention are the following ternary mixtures: 1) HFC-32, HFC-125 and HFO-1234ze; and 2) HFC-32, HFC-125 and HFO-1234yf.

By "ternary mixture" is meant a composition consisting essentially of the three compounds mentioned, that is to say in which the three compounds mentioned represent at least 99% (preferably at least 99.5% or even at least 99.9%). %) of the composition. Unless otherwise stated, in the whole of the application the proportions of compounds indicated are given in percentages by mass. HFO-1234ze can be in cis or trans form (preferably trans) or be a mixture of both forms. In the above compositions, HFC-32 is present in an amount of 5 to 50%, HFC-125 is present in an amount of 2 to 20% and HFO-1234yf or HFO-1234ze is present in an amount of 30%. at 90%. For use in low temperature refrigeration processes, i.e. those in which the temperature of the cooled fluid or body is -40 ° C to -10 ° C, and preferably -35 ° C at -25 ° C, more preferably from -30 ° C to -20 ° C (ideally about -25 ° C), it has been found that the most effective compositions replacing R404a are as follows: for composition 1): from 15 to 50% of HFC-32, from 5 to 20% of HFC-125 and from 30 to 80% of HFO-1234ze, and preferably from 30 to 40% of HFC-32, from 8 to 20% of HFC-32; 125 and 40 to 62% of HFO-1234ze; for composition 2): from 15 to 35% of HFC-32, from 5 to 20% of HFC-125 and from 45 to 80% of HFO-1234yf, and preferably from 18 to 25% of HFC-32, from 8 to 20% of HFC -125 and 55 to 74% of HFO-1234yf. For use in: moderate temperature cooling processes, i.e. those in which the temperature of the cooled fluid or body is -15 ° C to 15 ° C, preferably -10 ° C to 10 ° C, more preferably from -5 ° C to 5 ° C (ideally about 0 ° C), as well as moderate temperature heating processes, i.e. those in which the temperature fluid or heated body is 30 ° C to 80 ° C, and preferably 35 ° C to 55 ° C, more preferably 40 ° C to 50 ° C (most preferably about 45 ° C) , it has been found that the most effective compositions replacing HFC-134a are the following: for the composition 1): from 5 to 30% of HFC-32, from 5 to 20% of HFC-125 and from 50 to 90% HFO-1234ze, and preferably 5 to 20% HFC-32, 5 to 20% HFC-125 and 60 to 90% HFO-1234ze.

For use in: moderate temperature cooling processes, i.e. those in which the temperature of the cooled fluid or body is -15 ° C to 15 ° C, preferably -10 ° C to 10 ° C, more preferably from -5 ° C to 5 ° C (ideally about 0 ° C), as well as moderate temperature heating processes, i.e. those in which the temperature fluid or heated body is 30 ° C to 80 ° C, and preferably 35 ° C to 55 ° C, more preferably 40 ° C to 50 ° C (most preferably about 45 ° C) it has been found that the most effective compositions replacing R404a or R407c are as follows: for composition 1): from 20 to 40% of HFC-32, from 5 to 20% of HFC-125 and from 40 to 75% HFO-1234ze, and preferably 25 to 40% HFC-32, 5 to 20% HFC-125 and 40 to 70% HFO-1234ze; for composition 2): from 15 to 35% of HFC-32, from 5 to 20% of HFC-125 and from 45 to 80% of HFO-1234yf, and preferably from 18 to 25% of HFC-32, from 8 to 20% of HFC -125 and 55 to 74% of HFO-1234yf. In the "low temperature refrigeration" processes mentioned above, the inlet temperature of the heat transfer fluid to the evaporator is preferably from -45 ° C. to -15 ° C., especially from -40 ° C. at -20 ° C, more preferably -35 ° C to -25 ° C and for example about -30 ° C; and the temperature of the onset of condensation of the heat transfer fluid at the condenser is preferably 25 ° C to 80 ° C, especially 30 ° C to 60 ° C, more preferably 35 ° C to 55 ° C C and for example about 40 ° C. In the "moderate temperature cooling" processes mentioned above, the inlet temperature of the heat transfer fluid to the evaporator is preferably from -20 ° C. to 10 ° C., especially from -15 ° C. to 5 ° C, more preferably from -10 ° C to 0 ° C and for example about -5 ° C; and the temperature of the onset of condensation of the heat transfer fluid at the condenser is preferably 25 ° C to 80 ° C, especially 30 ° C to 60 ° C, more preferably 35 ° C to 55 ° C C and for example about 50 ° C. These processes can be refrigeration or air conditioning processes.

In the "moderate temperature heating" processes mentioned above, the inlet temperature of the heat transfer fluid to the evaporator is preferably from -20 ° C. to 10 ° C., in particular from -15 ° C. to 5 ° C, more preferably from -10 ° C to 0 ° C and for example about -5 ° C; and the temperature of the onset of condensation of the heat transfer fluid at the condenser is preferably 25 ° C to 80 ° C, especially 30 ° C to 60 ° C, more preferably 35 ° C to 55 ° C C and for example about 50 ° C. The heat transfer fluids mentioned above are not quasi-azeotropic and are very effective when properly coupled to a countercurrent heat exchanger (with a temperature difference with the second approximately constant fluid in the water). exchanger). Each above heat transfer fluid may be mixed with one or more additives to provide the heat transfer composition effectively flowing in the vapor compression circuit. The additives may especially be chosen from lubricants, stabilizers, surfactants, tracer agents, fluorescent agents, odorants, solubilizing agents and mixtures thereof.

The stabilizer (s), when present, preferably represent at most 5% by weight in the heat transfer composition. Among the stabilizers, there may be mentioned in particular nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenol compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-tert-butyl-4-methylphenol, epoxides (optionally fluorinated or perfluorinated alkyl or alkenyl or aromatic) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, phosphites, phosphonates, thiols and lactones. Lubricants that may be used include oils of mineral origin, silicone oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha olefins, polyalkene glycols, polyol esters and / or polyvinyl ethers. .

As tracer agents (which can be detected) mention may be made of hydrofluorocarbons, deuterated hydrofluorocarbons, deuterated hydrocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes and ketones. nitrous oxide and combinations thereof. The tracer agent is different from the one or more heat transfer compounds composing the heat transfer fluid. As solubilizing agents, mention may be made of hydrocarbons, dimethyl ether, polyoxyalkylene ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and the like. , 1-trifluoroalcanes. The solubilizing agent is different from the one or more heat transfer compounds composing the heat transfer fluid. As fluorescent agents, mention may be made of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanhthenes, fluoresceins and derivatives and combinations thereof. As odorants, mention may be made of alkyl acrylates, allyl acrylates, acrylic acids, acrylresters, alkyl ethers, alkyl esters, alkynes, aldehydes, thiols, thioethers, disulfides, allyl isothiocyanates and alkanoic acids. amines, norbornenes, norbornene derivatives, cyclohexene, heterocyclic aroma compounds, ascaridol, o-methoxy (methyl) phenol and combinations thereof.

The compositions according to the invention may also be useful as an expansion agent, aerosol or solvent.

EXAMPLES The following examples illustrate the invention without limiting it.

EXAMPLE 1 - METHOD OF CALCULATING THE PROPERTIES OF THE FLUIDS OF HEAT TRANSFER IN THE DIFFERENT CONSIDERATIONS INVESTIGATED The RK-Soave equation is used for calculating the densities, enthalpies, entropies and the liquid vapor equilibrium data of the mixtures. The use of this equation requires knowledge of the properties of the pure bodies used in the mixtures in question and also the interaction coefficients for each binary. The necessary data for each pure body are the boiling temperature, the critical temperature and the critical pressure, the pressure versus temperature curve from the boiling point to the critical point, the densities of saturated liquid and saturated steam as a function of temperature. The HFC data are published in the ASHRAE Handbook 2005 Chapter 20 and are also available under Refrop (Software developed by NIST for calculating the properties of refrigerants). The temperature-pressure curve data of the HFOs are measured by the static method. The critical temperature and the critical pressure are measured by a C80 calorimeter marketed by Setaram.

The saturation densities as a function of temperature are measured by the vibrating tube densimeter technology developed by the laboratories of the Ecole des Mines de Paris. The RK-Soave equation uses binary interaction coefficients to represent the behavior of products in mixtures. The coefficients are calculated based on the experimental vapor equilibrium data. The technique used for liquid vapor equilibrium measurements is the analytical static cell method. The balance cell includes a sapphire tube and is equipped with two electromagnetic ROLSITM samplers. It is immersed in a cryothermostat bath (HUBER HS40). Variable speed rotary field driving magnetic stirring is used to accelerate equilibrium attainment. The analysis of the samples is carried out by chromatography (HP5890 seriesll) in the gas phase using a katharometer (TCD).

The liquid vapor equilibrium measurements on the HFC-32 / HFO-1234ze binary are carried out for the following isotherm: 15 ° C. Liquid vapor equilibrium measurements on HFC-32 / HFO-1234yf are performed for the following isotherms: 70 ° C, 30 ° C, -10 ° C.

The liquid vapor equilibrium data for the HFC-32 / HFC-125 binary is available under Refprop. Three isotherms (-30 ° C, 0 ° C and 30 ° C) are used to calculate the interaction coefficients for this binary. The liquid vapor equilibrium measurements on the HFC-125 / HFO-1234yf binary are carried out for the following isotherms: -15 ° C., 0 ° C.

The liquid vapor equilibrium measurements on the HFC-125 / HFO-1234ze binary are carried out for the following isotherms: 25 ° C, 0 ° C. We consider a compression system equipped with an evaporator and countercurrent condenser, a screw compressor and a pressure reducer. The system operates with 15 ° C overheating and 5 ° C subcooling. The minimum temperature difference between the secondary fluid and the refrigerant is considered to be of the order of 5 ° C. The isentropic efficiency of the compressors is a function of the compression ratio. This yield is calculated according to the following equation: (1) 'lisen = ab (ti-c) Z_ di -e For a screw compressor, the constants a, b, c, d and e of equation (1) The isentropic efficiency is calculated according to the standard data published in the Handbook of air conditioning and refrigeration, page 11.52.

The coefficient of performance (COP) is defined as the useful power provided by the system on the power supplied or consumed by the system.

The Lorenz coefficient of performance (COPLorenz) is a benchmark coefficient of performance. It is temperature dependent and is used to compare the COPs of different fluids.

The coefficient of performance of Lorenz is defined as follows (the temperatures T are in K):

+ condenser _ + condenser _ + medium evaporatorx output condenser - Tevaporatexr _ Tevaporatexr average input output 35 (2) (3) The Lorenz COP in the case of air conditioning and refrigeration is: Tevaporatesr COPlorenz = average - + condenser _ Tevaporate medium average

The Lorenz COP in the case of heating is: T condensor COPlorenz = medium T condenser medium evaporator average For each composition, the coefficient of performance of the Lorenz cycle is calculated as a function of the corresponding temperatures.

In low temperature refrigeration mode, the compression system operates between a refrigerant inlet temperature

15 to the evaporator of -30 ° C and a refrigerant inlet temperature to the condenser of 40 ° C. The system supplied cold at -25 ° C.

In moderate heat mode, the compression system operates between a refrigerant inlet temperature at the evaporator of -5 ° C and a temperature at the beginning of the condensation of

Condenser refrigerant at 50 ° C. The system provides heat at 45 ° C.

In cooling mode at moderate temperature, the compression system operates between a refrigerant inlet temperature at the evaporator of -5 ° C and a temperature at the beginning of the condensation of the

Condenser refrigerant at 50 ° C. The system supplied cold at 0 ° C.

In the following tables, "evap outlet temperature" designates the fluid temperature at the outlet of the evaporator, "comp outlet temperature" designates the temperature of the fluid at the outlet of the compressor, "T output cond" designates the fluid temperature at the condenser outlet, "evap

P "refers to the fluid pressure in the evaporator," cond P "refers to the fluid pressure in the condenser," Rate (w / w) "refers to the compression ratio," Gide "refers to temperature slip," comp 'efficiency' means the efficiency of the compressor, '% CAP' means the volumetric capacity of the fluid in relation to the reference fluid indicated in

35 first line and "% COP / COPlrorenz" refers to the ratio of the system COP to the COP of the corresponding Lorenz cycle. (4) (5) Example 2 - Results for low temperature refrigeration, comparison with R404a

Mixture HFC-32 / HFC-125 / HFO-1234ze: Composition (%) d d C co ca o. : a C o N o o o o o o o o. UE O. Q aco 0 'o 9- C.) a o-., EE o UO y Q. E ô m U c c c c E> H oa) coi ~ LUH ow H R404A -30 100 40 2.1 18.1 8.8 0.46 53.8 100 32 M Ln 'NONM 30 50 20 -25 117 35 2.2 18.4 8.2 5.14 58.1 131 38 23 25 52 -23 112 32 1 , 6 13.4 8.4 7.36 56.9 103 40 35 8 57 -22 121 32 1.7 14.0 8.2 7.86 58.4 113 41 40 8 52 -22 125 32 1.8 14.9 8.1 7.70 59.2 121 42 35 12 53 -22 121 32 1.8 14.4 8.2 7.73 58.7 116 41 40 12 48 -22 124 32 1.9 15 3 8.1 7.53 59.4 124 42 30 16 54 -22 117 32 1.7 13.8 8.3 7.67 58.0 110 41 35 16 49 -22 120 32 1.8 14.7 8 , 1 7.58 59.0 118 41 40 16 44 -23 124 32 1.9 15.7 8.1 7.32 59.6 126 42 30 20 50 -22 117 32 1.7 14.2 8.2 7.56 58.4 113 41 35 20 45 -23 120 32 1.9 15.2 8.1 7.41 59.3 121 41 40 20 40 -23 124 33 2.0 16.1 8.1 7, In the preceding table, as in the following tables, the gray lines correspond to the compositions disclosed in the documents US 2009/0250650 or WO 2010/002014 and the following lines correspond to the compositions according to US Pat. 'invention. Mixture HFC-32 / HFC-125 / HFO-1234yf: Composition (%) d d C i i .-. : ## EQU1 ## where ## EQU1 ## Q UOO Q Q. E pm U aa .. to E o UE> H o c0 C c0 LH oa) coi ~ w H R404A -30 100 40 2.1 18.1 8.8 0.46 53, 8 100 32 '> + M Ln Omr LL ~ ce) = N 25 25 50 -28 114 37 2,3 19,7 8,6 2,39 55,7 125 35 60 15 25 -26 98 34 1,7 14 , 7 8.5 3.84 56.5 99 37 72 20 8 -25 100 33 1.7 14.4 8.3 3.63 58.1 102 39 70 22 8 -25 101 33 1.8 14.8 8.2 4.73 58.5 106 39 67 25 8 -25 103 33 1.9 15.4 8.1 4.79 59.0 111 39 62 30 8 -25 108 34 2.0 16.5 8, 1 4,68 59,2 119 39 70 18 12 -26 99 33 1,7 14,3 8,3 4,37 57,4 100 38 68 20 12 -25 100 33 1.8 14.7 8.3 4 , 50 58.0 104 38 66 22 12 -25 102 33 1.8 15.1 8.2 4.58 58.3 107 39 63 25 12 -25 104 33 1.9 15.8 8.2 4.61 58.7 113 39 66 18 16 -26 99 33 1.8 14.6 8.3 3.27 57.4 101 38 64 20 16 -26 101 33 1.8 15.0 8.3 4.3 37 57 8,105 38 62 22 16 -26 102 33 1.9 15.5 8.2 4.43 58.2 109 38 59 25 16 -26 105 34 2.0 16.1 8.2 4.43 58.4 114 39 62 18 20 -26 100 33 1.8 15.0 8.4 4.16 57.3 103 38 60 20 20 -26 101 33 1.9 15.4 8.3 4.24 57.7 107 38 58 22 20 -26 103 34 1.9 15.8 8.3 4.27 58.0 110 38 55 25 20 - 26 106 34 2.0 16.5 8.2 4.24 58.2 115 38 10 Example 3 - Results for Cooling at Moderate Temperature, Comparison with HFC-134a Mixture HFC-32 / HFC-125 / HFO-1234ze : Composition (%) dd ^ ^ ii Q. d - <N ^ O r U t0 l0 Q. = CC 0 oy Q- ô aa - d E QQ L y Q. E ° c.)> O c0 mo OJE acted H agi c °,) ~ LOHO R134a -5 81 50 2.4 13.2 5.4 0.00 75.9 100 54 ce). Ln 'N 0 N 0mr 2 () uM _ _ C1 15 80 -1 74 44 2.5 12.2 4.8 4.02 78.5 106 56 5 18 77 -1 74 44 2.6 12.4 4 , 7 4.27 78.7 109 56 5 20 75 -1 74 44 2.7 12.6 4.7 4.42 78.8 111 56 5 85 0 76 43 2.7 12.5 4.6 5, 10 79.1 116 58 10 15 75 1 77 43 2.9 13.3 4.5 5.52 79.5 124 57 10 18 72 1 77 43 3.0 13.6 4.5 5.64 79.6 127 57 10 20 70 1 76 43 3.1 13.7 4.5 5.72 79.6 128 57 5 80 1 79 42 3.1 13.5 4.4 6.32 79.8 132 58 15 15 70 1 79 42 3.3 14.4 4.3 6.43 80.0 139 58 15 18 67 1 79 42 3.4 14.7 4.3 6.47 80.1 142 58 15 20 65 2 79 42 3 , 5 14.9 4.3 6.50 80.1 144 58 5 75 2 81 42 3.4 14.6 4.3 7.01 80.2 146 59 20 15 65 2 81 42 3.7 15.5 4.2 6.95 80.4 154 58 5 10 15 Example 4 - Results for moderate temperature heating, comparison with HFC-134a

Mixture HFC-32 / HFC-125 / HFO-1234ze: Composition (%) ## STR1 ## m m O. a to y. w O. o o. a -x .ad Q 0 2 E> E Ho co c.) o c0 O 'a U o ° 0 H E0 agi ~ ~~ OHL R134a -5 81 50 2,4 13,2 5,4 0,00 75 , 9 100 63 O n NOM = r 15 80 -1 74 44 2.5 12.2 4.8 4.02 78.5 103 65 5 18 77 -1 74 44 2.6 12.4 4.7 4, 27 78.7 106 65 5 20 75 -1 74 44 2.7 12.6 4.7 4.42 78.8 108 65 5 85 0 76 43 2.7 12.5 4.6 5.10 79.1 110 66 10 15 75 1 77 43 2.9 13.3 4.5 5.52 79.5 118 66 10 18 72 1 77 43 3.0 13.6 4.5 5.64 79.6 121 66 10 20 70 1 76 43 3.1 13.7 4.5 5.72 79.6 123 66 5 80 1 79 42 3.1 13.5 4.4 6.32 79.8 124 66 15 15 70 1 79 42 3 , 3 14.4 4.3 6.43 80.0 132 66 15 18 67 1 79 42 3.4 14.7 4.3 6.47 80.1 135 66 15 20 65 2 79 42 3.5 14, 9 4.3 6.50 80.1 136 66 5 75 2 81 42 3.4 14.6 4.3 7.01 80.2 137 66 20 15 65 2 81 42 3.7 15.5 4.2 6 EXAMPLE 5 Results for Cooling at Moderate Temperature, Comparison with R404a and R407c

HFC-32 / HFC-125 / HFO-1234ze mixture: Composition (%) E ^ 2 ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ o., m 0 OJE agi E ° ~ c °,) c0 aa) OHH ~ L R404A -5 77 50 5.2 23.0 4.5 0.37 79.7 100 48 R407C -1 89 45 4.5 19.8 4.4 4.46 79.9 114 56 L_ NAME 30 50 20 0 89 45 5.7 23.6 4.2 4.88 80.5 133 54 23 25 52 2. 83 42 4.2 17, 3 4.1 7.04 80.6 109 58 25 5 70 2 84 42 3.8 15.7 4.2 7.38 80.5 102 59 25 15 60 2 84 42 4.0 16.7 4.1 7.23 80.6 107 59 30 5 65 3 87 42 4.1 16.8 4.1 7.54 80.7 110 59 40 5 55 2 92 42 4.7 18.9 4.0 7.45 80 , 9 124 59 40 15 45 2 92 43 5.0 20.1 4.0 7.04 80.9 129 58 40 18 42 2 92 43 5.1 20.5 4.0 6.88 80.9 131 58 40 20 40 2 92 43 5.2 20.8 4.0 6.77 80.9 132 58 10 15 20 5 Example 6 - Results for cooling at moderate temperature, comparison with R404a

Mixture HFC-32 / HFC-125 / HFO-1234yf: Composition (%) a) a)? ## EQU1 ## ## EQU1 ## 23.0 4.5 0.37 79.7 100 48 '~ + M IUiN OHM O = = N 52 23 25 -1 82 45 5.1 21.1 4.1 4.32 80.6 117 54 60 15 25 -1 76 44 4.5 18.8 4.2 3.23 80.5 104 54 74 18 8 0 77 43 4.4 17.9 4.1 4.97 80.7 104 56 72 20 8 0 78 43 4.5 18.5 4.1 5.11 80.8 107 56 70 22 8 0 79 43 4.7 19.0 4.1 5.18 80.8 111 56 67 25 8 0 81 43 4.9 19.8 4.0 5.18 80.8 115 56 62 30 8 0 84 44 5.2 21.1 4.1 4.97 80.8 122 55 70 18 12 0 77 43 4.5 18.3 4 , 1 4.84 80.7 105 55 68 20 12 0 78 43 4.6 18.8 4.1 4.95 80.7 108 55 66 22 12 0 80 43 4.8 19.4 4.1 4, 99 80.8 112 55 63 25 12 0 81 44 5.0 20.2 4.1 4.97 80.8 116 55 58 30 12 0 85 44 5.3 21.5 4.1 4.72 80.7 123 55 69 15 16 -1 76 43 4.3 17.9 4.2 4.47 80.6 100 55 66 18 16 0 77 43 4.5 18.7 4.1 4.70 80.7 106 55 64 20 16 0 79 44 4.7 19.3 4.1 4.78 80.7 109 55 62 22 16 0 80 44 4.8 19.8 4.1 4.80 80.7 113 55 59 25 16 0 82 44 5.0 20.6 4.1 4.75 80.7 117 55 65 15 20 -1 76 44 4.4 18.3 4.2 4.37 80.5 102 55 60 20 20 0 79 44 4.8 19.7 4.1 4.61 80.6 111 55 58 22 20 0 80 44 4.9 20.3 4.1 4.61 80 Example 7 - Results for moderate temperature heating, comparison with R404a

Mixture HFC-32 / HFC-125 / HFO-1234yf: Composition (%) a) a) Q: arv N ^ oov ° rv c0 c0 Q. C a o0 Q- ô a 2 KI ° Q .

5 O J yQ.Q. yQ. y that G-co ûd 0 0 o H o H c aa)) o ~ aa) OH c °,) L R404A -5 77 50 5.2 23.0 4.5 0.37 79.7 100 48 '> + M u 0Ln MON = N LL = 52 23 25 -1 82 45 5.1 21.1 4.1 4.32 80.6 110 63 60 15 25 -1 76 44 4.5 18.8 4.2 4 , 23 80.5 98 63 72 20 8 0 78 43 4.5 18.5 4.1 5.11 80.8 100 64 70 22 8 0 79 43 4.7 19.0 4.1 5.18 80 8,103 64 67 25 8 0 81 43 4.9 19.8 4.0 5.18 80.8 108 64 68 20 12 0 78 43 4.6 18.8 4.1 4.95 80.7 102 64 66 22 12 0 80 43 4.8 19.4 4.1 4.99 80.8 105 64 66 18 16 0 77 43 4.5 18.7 4.1 4.70 80.7 100 645

Claims (10)

REVENDICATIONS1. Ternary composition comprising: - from 5 to 50% of difluoromethane; from 2 to 20% of pentafluoroethane; and 30 to 90% of tetrafluoropropene. The composition of claim 1, wherein the tetrafluoropropene is 1,3,3,3-tetrafluoropropene. The composition of claim 1, wherein the tetrafluoropropene is 2,3,3,3-tetrafluoropropene. 4. Composition according to claim 1, comprising: - from 15 to 35% of difluoromethane; from 5 to 20% of pentafluoroethane; and from 45 to 80% 2,3,3,3-tetrafluoropropene; and preferably: 18 to 25% difluoromethane; from 8 to 20% of pentafluoroethane; and from 55 to 74% 2,3,3,3-tetrafluoropropene; The composition of claim 1 comprising: - 15 to 50% difluoromethane; from 5 to 20% of pentafluoroethane; and from 30 to 80% of 1,3,3,3-tetrafluoropropene; and preferably: from 30 to 40% difluoromethane; from 8 to 20% of pentafluoroethane; and from 40 to 62% of 1,3,3,3-tetrafluoropropene. 6. Composition according to claim 1, comprising: - from 5 to 30% of difluoromethane; from 5 to 20% of pentafluoroethane; and from 50 to 90% of 1,3,3,3-tetrafluoropropene; and preferably: from 5 to 20% of difluoromethane; 30 35 7. 5 10 8. 15 9. 20 10. 2511. 12.35- 5 to 20% pentafluoroethane; and from 60 to 90% of 1,3,3,3-tetrafluoropropene. The composition of claim 1 comprising: - from 20 to 40% difluoromethane; from 5 to 20% of pentafluoroethane; and from 40 to 75% of 1,3,3,3-tetrafluoropropene; and preferably: 25 to 40% difluoromethane; from 5 to 20% of pentafluoroethane; and from 40 to 70% of 1,3,3,3-tetrafluoropropene. Use of a composition according to one of claims 1 to 7 as a heat transfer fluid in a vapor compression circuit. A heat transfer composition comprising the composition according to one of claims 1 to 7 as a heat transfer fluid, and one or more additives selected from lubricants, stabilizers, surfactants, tracer agents, fluorescent agents, odorants, solubilizers and mixtures thereof. A heat transfer apparatus comprising a vapor compression circuit containing a composition according to one of claims 1 to 7 as heat transfer fluid or containing a heat transfer composition according to claim 9. Installation according to claim 10 , chosen from mobile or stationary heat pump heating, air conditioning, refrigeration and freezing installations. A method of heating or cooling a fluid or a body by means of a vapor compression circuit containing a heat transfer fluid, said method comprising successively evaporation of the heat transfer fluid, compression of the heat transfer fluid, the condensation of the heat medium and the expansion of the heat transfer fluid, wherein the heat transfer fluid is a composition according to one of claims 1 to 7. 13. The method according to claim 12, which is a method of cooling a fluid or a body, wherein the temperature of the cooled fluid or body is -40 ° C to -10 ° C, and preferably -35 ° C to -25 ° C C, more preferably from -30 ° C to -20 ° C, and wherein the heat transfer fluid comprises: - 15 to 35% difluoromethane, 5 to 20% pentafluoroethane and 45 to 80 % 2,3,3,3-tetrafluoropropene, preferably 18 25% difluoromethane, 8 to 20% pentafluoroethane and 55 to 74% 2,3,3,3-tetrafluoropropene; or - from 15 to 50% of difluoromethane, from 5 to 20% of pentafluoroethane and from 30 to 80% of 1,3,3,3-tetrafluoropropene, preferably from 30 to 40% of difluoromethane, from 8 to 20% of pentafluoroethane and from 40 to 62% 1,3,3,3-tetrafluoropropene. The method of claim 12, which is a method of cooling a fluid or a body, wherein the temperature of the cooled fluid or body is from -15 ° C to 15 ° C, and preferably from 10 ° C to 10 ° C, more preferably -5 ° C to 5 ° C, and wherein the heat transfer fluid comprises: 15 to 35% difluoromethane, 5 to 20% pentafluoroethane, and from 45 to 80% of 2,3,3,3-tetrafluoropropene, preferably from 18 to 25% of difluoromethane, from 8 to 20% of pentafluoroethane and from 55 to 74% of 2,3,3,3-tetrafluoropropene; or 5 to 30% of difluoromethane, 5 to 20% of pentafluoroethane and 50 to 90% of 1,3,3,3-tetrafluoropropene, preferably 5 to 20% of difluoromethane, 5 to 20% of pentafluoroethane and from 60 to 90% 1,3,3,3-tetrafluoropropene; or 20 to 40% of difluoromethane, 5 to 20% of pentafluoroethane and 40 to 75% of 1,3,3,3-tetrafluoropropene, preferably 25 to 40% of difluoromethane, 5 to 20% pentafluoroethane and 40 to 70% 1,3,3,3-tetrafluoropropene. The method of claim 12, which is a method of heating a fluid or a body, wherein the temperature of the fluid or heated body is 30 ° C to 80 ° C, and preferably 35 ° C. At 55 ° C, more preferably from 40 ° C to 50 ° C, and wherein the heat transfer fluid comprises: 15 to 35% difluoromethane, 5 to 20% pentafluoroethane and 45 to 80% of 2,3,3,3-tetrafluoropropene, preferably 18 to 25% of difluoromethane, 8 to 20% of pentafluoroethane and 55 to 74% of 2,3,3,3-tetrafluoropropene; or 5 to 30% of difluoromethane, 5 to 20% of pentafluoroethane and 50 to 90% of 1,3,3,3-tetrafluoropropene, preferably 5 to 20% of difluoromethane, 5 to 20% of pentafluoroethane and from 60 to 90% 1,3,3,3-tetrafluoropropene; or 20 to 40% of difluoromethane, 5 to 20% of pentafluoroethane and 40 to 75% of 1,3,3,3-tetrafluoropropene, preferably 25 to 40% of difluoromethane, 5 to 20% of pentafluoroethane and 40 to 70% 1,3,3,3-tetrafluoropropene. A method of reducing the environmental impact of a heat transfer facility comprising a vapor compression circuit containing an initial heat transfer fluid, said method comprising a step of replacing the initial heat transfer fluid in the vapor compression circuit by a final transfer fluid, the final transfer fluid having a GWP lower than the initial heat transfer fluid, wherein the final heat transfer fluid is a composition according to one of claims 1 to 7 17. The process according to claim 16, wherein the initial heat transfer fluid is a ternary mixture of 52% 1,1,1-trifluoroethane, 44% pentafluoroethane and 40% 1,1, 1,2-tetrafluoroethane or a ternary mixture of 52% 1,1,1,2-tetrafluoroethane, 25% pentafluoroethane and 23% difluoromethane, and wherein the final heat transfer fluid comprises : 15 to 35% of difluoromethane, 5 to 20% of pentafluoroethane and 45 to 80% of 2,3,3,3-tetrafluoropropene, preferably 18 to 25% of difluoromethane, 8 to 20% of pentafluoroethane and 55 to 74% 2,3,3,3-tetrafluoropropene; or 15 to 50% of difluoromethane, 5 to 20% of pentafluoroethane and 30 to 80% of 1,3,3,3-tetrafluoropropene, preferably 30 to 40% of difluoromethane, 8 to 20% of pentafluoroethane and from 40 to 62% 1,3,3,3-tetrafluoropropene; or 20 to 40% of difluoromethane, 5 to 20% of pentafluoroethane and 40 to 75% of 1,3,3,3-tetrafluoropropene, preferably 25 to 40% of difluoromethane, 5 to 20% of pentafluoroethane and 40 to 70% 1,3,3,3-tetrafluoropropene. 18. The method of claim 16, wherein the initial heat transfer fluid is 1,1,1,2-tetrafluoroethane, and wherein the final heat transfer fluid comprises: - from 5 to 30% difluoromethane from 5 to 20% of pentafluoroethane and from 50 to 90% of 1,3,3,3-30 tetrafluoropropene, preferably from 5 to 20% of difluoromethane, from 5 to 20% of pentafluoroethane and from 60 to 90% of 1,3,3,3-tetrafluoropropene. 10 15 20